CN102858859B - Polylactic acid composition, foam-molded article thereof and method for producing same - Google Patents

Polylactic acid composition, foam-molded article thereof and method for producing same Download PDF

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CN102858859B
CN102858859B CN201180016776.7A CN201180016776A CN102858859B CN 102858859 B CN102858859 B CN 102858859B CN 201180016776 A CN201180016776 A CN 201180016776A CN 102858859 B CN102858859 B CN 102858859B
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poly
lactic acid
composition
polyisocyanates
molded product
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CN102858859A (en
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内山幸助
津田和典
铃木天也
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White Gull Logical Ltd By Share Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/58—Moulds
    • B29C44/586—Moulds with a cavity increasing in size during foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/365—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps
    • B29C48/37—Gear pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/64—Screws with two or more threads
    • B29C48/655—Screws with two or more threads having three or more threads
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/428—Lactides
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
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    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/76—Venting, drying means; Degassing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

The object is to economically provide a method and device for producing a high-viscosity polylactic acid composition which is stable and suitable for foam-molding at a high expansion ratio, and a foam-molded article with a high expansion ratio which is formed of said polylactic acid composition. The above object can be achieved by a method for producing a foam-molded article of polylactic acid characterized by involving a step for using a device provided with an injection molding machine (B) or an extrusion molding machine (G), an orifice part (S) and a foaming mold (P) and mechanically grinding a polylactic acid composition by, in a foaming gas atmosphere, applying a shear force to the polylactic acid composition in the orifice part (S). The aforesaid polylactic acid composition is obtained by mechanically grinding polylactic acid, that has been crosslinked by polyisocyanate, by applying a shear force thereto in an inert gas atmosphere. The aforesaid method is characterized in that the polylactic acid composition, which is obtained by the grinding as described above, has an MI of 0.05 to 5 inclusive, when measured at 190oC under a load of 21.6 kg in accordance with JIS K7210 (ISO 1133).

Description

Poly (lactic acid) composition, its foam molded product and manufacture method
Technical field
The present invention relates to poly (lactic acid) composition, expanded polylactic acid products formed and foam molded product manufacture method thereof.
Background technology
Poly(lactic acid), owing to being that starch by as regenerative raw materials is manufactured, has Biodegradable, so be environment amenable resin.Owing to thering is Biodegradable with the product of poly(lactic acid) manufacture, so can be as mixed fertilizer landfill discarded.
Foamed polystyrene products formed is used for greatly food product containers, amortizing packaging material etc., but owing to not being Biodegradable, so must recycle the waste or regenerate.
In patent documentation 1, recorded a kind of method, substantially for adding the polycarboxylic acids such as the polyvalent alcohols such as glycerine, tetrahydroxybutane and tetramethylolmethane or trimellitic acid and Pyromellitic Acid in the raw poly(lactic acid) of amorphous, with polyisocyanates, be cross-linked, improve molecular weight, manufacture foam molded product.
For making poly (lactic acid) composition obtain stable melt viscosity, the condition that meets following formula is better.
(0.5xn-100EM i)M c/10NM i≤W≤(0.5xn-100EM i)M c/NM i
(wherein, E: the terminal carboxyl(group) number (equivalent/gr) of poly(lactic acid)
X: isocyanate compound addition (% by weight)
N: functional group's number of isocyanate compound (equivalent/mole)
M i: the molecular weight of isocyanate compound (gr)
W: the addition of polyvalent alcohol or polycarboxylic acid (% by weight)
N: functional group's number of polyvalent alcohol or polycarboxylic acid (equivalent/mole)
M c: the molecular weight of polyvalent alcohol or polycarboxylic acid (gr))
This be due to, while only having poly(lactic acid), be difficult to obtain be suitable for the stable composition of the high melt viscosity of foaming and molding.
In addition, the use level of polyisocyanates is 0.3～3 % by weight, is preferably 0.7～2 % by weight better.If the polyisocyanates deficiency molecular weight of reacted poly(lactic acid) is too small, only obtain the foam molding of low expansion ratio.On the other hand, the foam molding can not get if polyisocyanates surplus gelation occurs.
After foam molded product infiltration whipping agent, with the pearl conveyance of pre-frothing, send in mould, with water vapour, heat and foaming and molding.As whipping agent, can use the ethers such as the halogenated hydrocarbons such as the hydro carbons such as propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, hexane, methyl chloride, methylene dichloride, Refrigerant 12, dimethyl ether, methyl ethyl ether as whipping agent, in addition, can use the alcohol, ketone, ether, benzene, toluene etc. of carbonatoms 1～4 as frothing aid.
In patent documentation 2, recorded in order to form homogeneous and fine abscess preferably coordinates foaming nucleation agent, as the foaming nucleation agent of using, the salt such as an alkali metal salt of the particle shape thing of solid state, inorganic particulate, carbonic acid or hydrocarbonate such as talcum, silicon-dioxide, kaolin, zeolite, mica, aluminum oxide, carboxylic acid are suitable.
In the manufacturing process of the polycarboxylic acids such as the polyvalent alcohols such as interpolation glycerine, tetrahydroxybutane and tetramethylolmethane of recording in patent documentation 1 or trimellitic acid and Pyromellitic Acid, must make polyisocyanates and poly(lactic acid) hybrid reaction in the 1st stage, at the 2nd stage interpolation polyvalent alcohol or polycarboxylic acid, carry out hybrid reaction.If make the order inversion of these reactions or react simultaneously, can there is gelation.
In order to make polyvalent alcohol or polycarboxylic acid append reaction in the 2nd operation by above-mentioned manufacturing process, need additional facility investment, manufacturing process is also elongated, so be disadvantageous economically.
In addition, so owing to using non-crystalline poly(lactic acid) to have the great like this shortcoming of thermotolerance deficiency of foam molded product.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2000-169546 communique
Patent documentation 2: TOHKEMY 2000-17039 communique
Summary of the invention
Invent problem to be solved
The high magnification foam molded product that the object of the invention is to provide at an easy rate the manufacture method of the stable high viscosity poly (lactic acid) composition that is suitable for high magnification foaming and molding and device and formed by it.
For the scheme of dealing with problems
Poly (lactic acid) composition of the present invention, it is characterized in that, it is by applying shearing force carry out mechanical disintegration and obtain poly (lactic acid) composition under the atmosphere of rare gas element having carried out crosslinked poly(lactic acid) with polyisocyanates, and the MI value that the poly (lactic acid) composition obtaining by above-mentioned pulverizing is measured according to JIS K7210 (ISO 1133) under 190 ℃, load 21.6kg is more than 0.05 and below 5.
In addition the manufacture method of the expanded polylactic acid products formed of preferred 1 mode of the present invention of conduct is a kind of manufacture method of foam molded product, it is characterized in that, comprise following operation: use the device that possesses injection moulding machine (B) or extrusion shaping machine (G), nib portion (S) and foaming mould (P), under foamed gas atmosphere, in nib portion (S), apply shearing force, above-mentioned poly (lactic acid) composition is carried out to mechanical disintegration.
The effect of invention
Poly (lactic acid) composition of the present invention is owing to not becoming the gelation part of essential factor or the poly(lactic acid) portion of remarkable large molecular weight of hindering when high magnification foam, thus can be by the attenuation of abscess film, can stablize and supply with at an easy rate high magnification foam molded product.In addition, using the foam molded product of the present invention of the poly (lactic acid) composition do not add polyvalent alcohol or polycarboxylic acid and stable high melt viscosity is foam molded product sheet material and the container of practical upper ability hot water.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of nib portion (S), becomes and between upper and lower pressing plate, clamps feeler gauge and be arranged on the structure on nozzle with bolt and nut.The feeler gauge thickness using in experiment for 0.1mm, be spaced apart 0.1mm, length is 150mm.
Fig. 2 is the simple schematic diagram of the processing machine system used in the embodiment of directly extrusion foaming injection.
Fig. 3 is the simple schematic diagram of the processing machine system used in the embodiment of direct extrusion foaming sheet forming.
The simple schematic diagram of (B) when (A), mobile protuberance are expanded the foaming of hollow bulb when Fig. 4 is the filling of hollow bulb thinner thickness in hollow bulb variable thickness foaming mould cross section.
Fig. 5 means the shape (A) of the screw front end portion possessing in the injection moulding machine shown in Fig. 2 or Fig. 3 (B) or forcing machine (G) and the 50mm of helical pitch thereof, the figure of groove configuration example (B) of 12.
Embodiment
Poly (lactic acid) composition of the present invention, it is characterized in that, it is by applying shearing force carry out the poly (lactic acid) composition that mechanical disintegration obtains under the super critical condition of rare gas element having carried out crosslinked poly(lactic acid) with polyisocyanates, with respect to poly(lactic acid), the use level of described polyisocyanates is 0.4～5 % by weight, and the MI value that the poly (lactic acid) composition obtaining by above-mentioned pulverizing is measured according to JISK7210 (ISO 1133) under 190 ℃, load 21.6kg is more than 0.05 and below 5.
In addition, 1 mode of the present invention is that above-mentioned polyisocyanates is triisocyanate, tetraisocyanate or vulcabond, or any the poly (lactic acid) composition in the adducts that comprises above-mentioned polyisocyanates.
In addition 1 mode of the present invention is the calcium carbonate that contains 0.5～5 % by weight or the above-mentioned poly (lactic acid) composition of talcum particulate.
In addition 1 mode of the present invention is the foam molded product being formed by above-mentioned poly (lactic acid) composition.Foam molded product has pre-frothing pearl is formed to the products formed of foaming and do not make pearl and the foam molded product of direct extrusion molding.
In addition 1 mode of the present invention is by after in the hot water injection moulding product container of 90 ℃ 3 minutes, indeformable and keep the foam molded product of the excellent heat resistance of container form.
The manufacture method of the expanded polylactic acid products formed of 1 mode of the present invention is a kind of manufacture method of foam molded product, it is characterized in that, comprise following operation: use the device that possesses injection moulding machine (B) or extrusion shaping machine (G), nib portion (S) and foaming mould (P), under foamed gas super critical condition, in nib portion (S), apply shearing force, above-mentioned poly (lactic acid) composition is carried out to mechanical disintegration.
Another 1 mode of the present invention is that to manufacture polyisocyanates be triisocyanate, tetraisocyanate or vulcabond, or by any in the adducts of above-mentioned polyisocyanates, carries out the method for the poly (lactic acid) composition foam molded product that crosslinked thickening forms.
Another 1 mode of the present invention is the method for foam molded product of being manufactured by the poly (lactic acid) composition that coordinates the above-mentioned thickening of 0.4 to 5 % by weight polyisocyanates with respect to poly(lactic acid).
Another 1 mode of the present invention is the method for foam molded product of being manufactured by the poly (lactic acid) composition of the above-mentioned thickening that contains 0.5～5 % by weight calcium carbonate or talcum particulate.
Isocyanic ester, because reactivity is large, so react with low-molecular-weight polyvalent alcohol or polycarboxylic acid, generates gel compound.And the reacting of terminal group as long as that amount of isocyanate is the not superfluous eyed structure that is just unlikely to generate gelation with high molecular reaction.But, although be unlikely to generate the huge eyed structure cannot not becoming moltenly, become heterogeneity reaction and generate significantly large molecule of molecular weight.If partly existing with the polystyrene conversion molecular weight that GPC measures is more than 2,000,000 polymers, the stretching that produces abscess film is uneven, and high magnification foaming becomes difficult.More preferably not comprising polystyrene conversion molecular weight is more than 1,500,000 high molecular compositions.
In patent documentation 1, infer the stability that lacks viscosity due to this significantly large polymer, thus polyvalent alcohol or polycarboxylic acid added, thus there is balanced reaction, reduce significantly large high molecular molecular weight and obtain stable abscess film.If do not use polyvalent alcohol or polycarboxylic acid use single methanol or monocarboxylic acid molecular weight reduce and to become significantly, become and put the cart before the horse.
Present inventor finds, by being reacted to the remarkable large polymer generating with the heterogeneity of above-mentioned isocyanic ester, utilization carries out fragmentation by superflow under rare gas element super critical condition, thereby reduce remarkable large high molecular molecular weight and obtain stable abscess film, further find, even coordinate 5 % by weight polyisocyanates with respect to poly(lactic acid), in crosslinking reaction under overcritical, under subcritical, do not confirm gel yet, finally complete the present invention.
In the present invention in order to produce large like this shearing force, under the supercritical state of nitrogen, poly (lactic acid) composition for example be take at a high speed, by the shape of pulverizing portion by the front end during as 50mm for for example screw diameter shown in Fig. 5 and the nib portion (S) of the formation of the slit being comprised of (1), (2), (3) as shown in Figure 1, the slit portion of 0.1mm, length 150mm in length and breadth.If it is 100, the 000cm/30 high speed of second (33m/ second) that this speed take by the composition of for example 10ml that the stroke in 30 seconds extrudes.Were it not for nib portion (S), while only consisting of the pulverizing portion of screw front end, grindability reduces terrifically.Screw rod external diameter is 50mm and raw material while being poly(lactic acid), and irrelevant with used rare gas element, the design temperature of this portion is preferably the scope of 160 to 180 ℃, conventionally, the pressure of this portion in the scope of 6～12MPa with the input amount balance of raw material.Yet, if the poly(lactic acid) of the quantity not sufficient raw material of rare gas element cannot can not taken in raw material in screw rod certainly with at a high speed by nib (S), be only from nib (S), to spill unrestrained on a small quantity.Conclusion is, confirm that 160 ℃ of above, conditions more than 6MPa are for meeting fully the numerical value of the super critical condition (147 ℃, 3.39MPa) of nitrogen, the relevant temperature of postcritical this portion of the present invention and the condition of pressure are confirmed to be 160～170 ℃, 6～12MPa and turn round.
While infiltrating whipping agent in poly(lactic acid) pearl, heat and under high pressure infiltration.If poly(lactic acid) is crystallinity, cause at this moment crystallization, can form crystallite network.The fusing point of poly(lactic acid) is generally more than 160 ℃, and the water vapour of the normal pressure using during final foaming is below 100 ℃.The crystallite generating when infiltration whipping agent hinders for becoming the stretching of the abscess film of high foamability.Therefore, use amorphism poly(lactic acid).
On the other hand, amorphism poly(lactic acid) thermotolerance is low, can not in adding the container of hot water, use.If the network that crystalline poly(lactic acid) is formed by crystallite improves thermotolerance and can be used in hot water vessel.By the way the material of the part white of PET bottleneck is because crystallization forms spherocrystal.So the part of bottleneck does not have crystallization owing to not stretching.After blow molding, heating makes its crystallization and gives thermotolerance.
The easy mobility of thermotolerance and molecule is inversely proportional.If molecule quantitative change greatly thermotolerance improves.Whiteruss is aqueous at normal temperatures, but the paraffin that molecular weight increases is a little solid at normal temperatures.Molecular weight further becomes large poly fusing point and becomes 130 ℃ of left and right.The fusing point of ultrahigh molecular weight polyethylene(UHMWPE) rises to 150 ℃.Principle with roll little snowball and roll not being both of the large needed power of snowball identical.
Poly(lactic acid) is owing to being polycondensate, so molecular weight changes according to equilibrium water component.Even the poly(lactic acid) of high molecular, also causes sharp that if be melted after moisture absorption molecular weight reduces, and is reduced to the balance molecular weight conforming to amount of moisture.Therefore, preferably in the melting initial stage of forcing machine, ventilation hole is set and absorbs moisture by vacuum pump.
The poly(lactic acid) of using in the present invention can be that crystalline polylactic acid can be also amorphism poly(lactic acid).The amorphism poly(lactic acid) of using the copolymerization of DL body to form when the pre-frothing pearl of infiltration whipping agent.While using crystalline polylactic acid when foam shaping by extrusion, thermotolerance improves, so preferably.In addition, the compound poly(lactic acid) that D body and L body are mixed improves thermotolerance more, so preferably.
The number-average molecular weight of above-mentioned raw materials polylactic acid raw material is preferably more than 1000, more preferably more than 5000, more preferably more than 10,000.The less polyisocyanates reacting in order to obtain required viscosity when high foamability moulding of molecular weight of raw material poly(lactic acid) coordinates quantitative change many, becomes economically unfavorable.
In addition, in the number-average molecular weight of being carried out the poly(lactic acid) of open loop solution polymerization by lactic acid dipolymer, be that 10,000 polyisocyanates liquid or the Low Temperature Thermals that add 0.5～5 % by weight when following dissolve liquid in advance, as LDPE, more than 500,000 poly(lactic acid) of number-average molecular weight that is polymerized to of branch can be used as the polylactic acid raw material that the present invention uses and uses.
Raw material poly(lactic acid) is dried by ordinary methods such as vacuum-dryings in advance, controls moisture rate.Raw material poly(lactic acid) moisture rate is preferably below 500ppm, more preferably below 100ppm.More preferably below 50ppm.Polyisocyanates, owing to also reacting with water, produces carbonic acid gas, becomes inertia, so the deterioration of efficiency of polyisocyanates.If it is disadvantageous at most economically that the moisture rate of raw material poly(lactic acid) is crossed.
The polyisocyanates using in the present invention is polyisocyanates more than divalent, preferably contains the adducts of triisocyanate or tetraisocyanate or vulcabond.If polyisocyanates more than 3 valencys of use produces branch on poly(lactic acid) macromolecular chain, film toughness becomes firmly, can improve expansion ratio.
Polyisocyanates is so long as have the isocyanate compound of 2 above isocyanate group in molecule.As polyisocyanates, for example have 1,6-hexamethylene diisocyanate, 3-isocyanic ester methyl-3,5,5-3-methyl cyclohexanol based isocyanate (isophorone diisocyanate), Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, methylcyclohexyl-2,4-vulcabond, methylcyclohexyl-2,6-vulcabond, xylylene vulcabond, two (isocyanic ester) methylcyclohexanes of 1,3-, tetramethyl-benzene dimethyl vulcabond, trans cyclohexane-Isosorbide-5-Nitrae-vulcabond, the aliphatic diisocyanates such as lysinediisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenation of benzene dimethyl vulcabond, hydrogenation tetramethyl-benzene dimethyl vulcabond, the alicyclic polyisocyanates such as cyclohexyl diisocyanate, 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, ditan-4,4 '-isocyanic ester, 1,5 '-cycloalkanes vulcabond, tolidine vulcabond, diphenyl methyl methane diisocyanate, tetraalkyl diphenylmethanediisocyanate, 4,4 '-dibenzyl vulcabond, the aromatic diisocyanates such as 1,3-phenylene diisocyanate, Methionin ester triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanic ester-4,4-isocyanic ester methyloctane, 1,3,6-hexa-methylene triisocyanate, bicycloheptane triisocyanate, the adducts of TriMethylolPropane(TMP) and 2,4 toluene diisocyanate, the triisocyanate compounds such as adducts of the vulcabond such as TriMethylolPropane(TMP) and 1,6-hexamethylene diisocyanate, and make glycerine, the polyvalent alcohols such as tetramethylolmethane and above-mentioned aliphatics and aromatic diisocyanate compounds and above-mentioned triisocyanate compound etc. react and modified polyisocyanate compound of obtaining etc.They can use separately a kind or two or more mix is used.
Polyisocyanates, by using polyisocyanates more than 3 valencys, produces branch on polylactic acid molecule chain, and abscess film toughness increases, so preferably.This phenomenon when by polyethylene film, is compared with the high density polyethylene(HDPE) of straight chain shape, and the Low Density Polyethylene on macromolecular chain with branch is more suitable is identical.
The use level of polyisocyanates is according to the molecular weight of raw material poly(lactic acid) and difference.In addition, also according to the molecular weight distribution of poly(lactic acid) and difference.If low molecular weight becomes at most in order to obtain being applicable to the more poly(lactic acid) use level of melt viscosity needs of foaming.Preferably with respect to poly(lactic acid), be approximately 0.5 % by weight～5 % by weight.If the use level of polyisocyanates is crossed and be can not get being at least applicable to the melt viscosity of foaming and reduce expansion ratio.In addition, even if too much also produce gelation, expansion ratio reduces.
Manufacturing process as poly (lactic acid) composition of the present invention, after the molecular weight of the poly (lactic acid) composition being brought by the linked reaction of utilizing poly(lactic acid) and polyisocyanates increases, under the super critical condition of rare gas element, mechanically applying large shearing force, remarkable large polylactic acid molecule is carried out to broken operation is necessary.If not this operation significantly large polylactic acid molecule hinder partly the expansion of abscess film, can not obtain high magnification foam molded product.
As the so-called rare gas element not reacting with poly(lactic acid) in the present invention, can list nitrogen, helium, argon gas, methane gas, ethane gas, propane gas, butane gas, ethylene gas, propylene gas etc.Wherein preferably easily reach super critical condition, cheapness and there is no flammable nitrogen.Sometimes also by these gases use.The super critical point of nitrogen is (147 ℃, 3.39MPa), and methane gas is (83 ℃, 4.6MPa).Ethane gas is (32.4 ℃, 4.88MPa).Propane gas is (93.8 ℃, 4.25MPa).Butane gas is (152 ℃, 3.38MPa).When manufacturing pearl, rare gas element is according to coordinate the mode weight feed of 0.1～2 % by weight with respect to raw material poly(lactic acid), but after trapping moisture, reclaims and reuse.
More than the pressure of the super critical point general method of being forced into, such as there being the pressurizing devices such as ram pump, toothed gear pump, screw rod, being heated and to the temperature of super critical point, is had above the heating units such as casting well heater or jacket heater.
The fusing point of poly(lactic acid) is also according to copolymerization degree and difference, but is approximately below 170 ℃.More than the fusing point of the polylactic acid raw material of using in the present invention react with polyisocyanates.The non-aqueous polyisocyanates melting of heating at normal temperatures in the present invention, adds in the polylactic acid raw material of semi-melting state quantitatively with ram pump etc., reacts with poly(lactic acid).When high viscosity reactant is mixed with lowering viscousity compound, by high viscosity thing at low temperatures, disperse fully in advance while mixing with semi-melting state, can expect to react more uniformly.
In poly (lactic acid) composition of the present invention, the polymkeric substance that is used in conjunction with other Biodegradable in remarkable dysgenic scope can not caused to foam molded product, to the physical property of foam molded product yet.As other Biodegradable polymkeric substance, there is such as polycaprolactam, polybutylene succinate, poly butyric ester, poly-(butyric ester/hydroxycaproic ester), (poly(lactic acid)/polybutylene succinate system) segmented copolymer, poly-(caprolactone/butylene succinate), poly-(succsinic acid/tetramethylene adipate), poly-(succsinic acid/carbonic acid butanediol ester), poly-(terephthalic acid/succsinic acid glycol ester), poly-(hexanodioic acid/mutual-phenenyl two acid bromide two alcohol ester), poly-(tetramethylene adipic acid ester/terephthalate) etc.
In order to form even and fine abscess, preferably coordinate foaming nucleation agent.As foaming nucleation agent, there is an alkali metal salt of the carbonic acid such as inorganic particulates such as talcum, silicon-dioxide, kaolin, zeolite, mica, aluminum oxide, calcium carbonate or hydrocarbonate, carboxylic acid etc.In them, calcium carbonate, talcum softness, can obtain minuteness particle at an easy rate, so preferably.In high magnification foaming because foaming abscess thickness diminishes, so the particle diameter of foaming nucleation agent be preferably below 1 μ m, more preferably below 0.5 μ m.The use level of foaming nucleation agent is preferably 0.5～5 % by weight with respect to poly (lactic acid) composition.If the use level of foaming nucleation agent is crossed the size of abscess at least and easily become inhomogeneous, if cross to become at most, be difficult to obtain high foamability.
In the present invention, the foaming rare gas element side direction such as nitrogen are injected in the poly (lactic acid) composition of the present invention of molten state, make its foaming.If now carry out foaming and molding under the super critical point of the foaming rare gas elementes such as nitrogen or high temperature more than undercritical conditions, condition of high voltage, can obtain the foam molded product of finer abscess, so preferably.Foaming rare gas element, except nitrogen, has the ethers such as halogenated hydrocarbon, dimethyl ether, methyl ethyl ether such as hydrocarbon such as propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, hexane, butane as whipping agent, methyl chloride, methylene dichloride, Refrigerant 12 etc.In addition as frothing aid, use the alcohol, ketone, ether, benzene, toluene of carbonatoms 1～4 etc.Also these whipping agents can be mixed and use.
Foam molded product manufacturing system of the present invention, as easy system example as shown in Figure 2, becomes the formation of injection moulding machine (B), Henschel mixer (L), hopper (A), nib portion (S), foaming mould (P).
The hollow bulb of the foaming mould using in the present invention (P) is movable.Be applicable to the simple situation of shape of product, be not suitable for shape of product complicated situation.In the 1st stage, for example, start to inject molten polymer under the state (0.1mm, Fig. 4 A) of the thin thickness of hollow bulb, in the 2nd stage, is extended at leisure net shape (Fig. 4 B).The temperature of polymkeric substance is reduced to 100 ℃ of following suitable temperature, and polymkeric substance occurs to solidify simultaneously,, according to the mode that reaches the expansion ratio of regulation, measures injection of polymer therebetween.With the time of 30 seconds～1 minute, more than the softening temperature of polymkeric substance, make its foaming, cooling and fixing, thus obtain regulation foamed products.In this injection molding cycle, there is foaming and cooling time in due to the cycle, so the injection molding cycle is compared elongated with general only cooling cycle.
Manufacturing system when products formed of the present invention is continuous foamed sheet material becomes the formation that general known T mould connects, and replaces the mould junctor (F) shown in Fig. 3 and foaming mould (P).
In above-mentioned products formed, can the quality of Biodegradable or foam molded product not had to the additives such as pigment, fire retardant, reodorant, stablizer, antiseptic-germicide, mould inhibitor that uses general use in influential scope yet.
In the mensuration of MI value of the present invention, for the reacted poly (lactic acid) composition of polyisocyanates, at die throat diameter, be that 2mm, nib length are under 10mm, 190 ℃, the condition of load 21.6kg, for raw material poly(lactic acid), at die throat diameter, be that 1mm, nib length are under the condition of 10mm, load 2.16kg, according to JIS K7210 (ISO 1133), be determined at weight g mobile in 10 minutes or 10 minutes converted weight g.Expansion ratio cuts out foam molded product 1ml in measuring, and gravimetry g1, cuts out poly (lactic acid) composition 1ml of the present invention, and gravimetry g2, obtains divided by the business of g1 as g2.The moisture rate of raw material poly(lactic acid) etc. is measured by Fischer's method.About the thermotolerance of foam molded product, in box products formed, inject the hot water of 90 ℃ until 80% degree of depth, by after 3 minutes also indeformable situation be judged to be well.Similarly inject boiling water, by after 3 minutes also indeformable situation be judged to be excellence.The situation of seeing distortion after injecting hot water is as bad.
Significantly large high molecular mensuration is to measure PSt conversion molecular weight distribution with GPC.
About details, further by embodiment, describe.
Embodiment
(Production Example 1)
By commercially available L-rac-Lactide, re-crystallizing in ethyl acetate purifying for D-rac-Lactide.Using L-rac-Lactide 90 weight parts of purifying, D-rac-Lactide 10 weight parts and as stannous octoate 0.5 weight part of catalyzer, drop in the autoclave with stirrer, reduce pressure degassed after, at N 2under atmosphere, carry out ring-opening polymerization under the polymerizing condition of 190 ℃, 0.5 hour, 1 hour, 2 hours.After having reacted, from autoclave, polymkeric substance is taken out with rod shape, after quenching, with rotary knife cutter, cut off, thereby manufacture raw material poly(lactic acid) particle.By this particle at 80 ℃ in Vacuumdrier after dry 24 hours, pack in the aluminium bag of nitrogen sealing and take care of and use.Use moisture rate for the poly(lactic acid) below 100ppm is as raw material poly(lactic acid).Polymerization time is that under the load 2.16kg of 0.5 hour, 1 hour, 1.5 hours sample P 0.5, P1, P1.5, MI value is respectively 800,420,88.
(embodiment 1) injection expansion molding
Use the manufacturing system of the formation shown in Fig. 2.The processing machine forming with ram pump (E), nib portion (S), foaming mould (P) is supplied with in use by Henschel mixer for mix and blend (L), hopper (A) for raw material supplying, injection moulding machine (B), foamed gas.
Use the easy processing machine system shown in Fig. 2, the MI value of manufacturing in Production Example 1 is respectively by 1 of Normal Atmospheric Temperature Liquid in 800,420,88 raw material poly(lactic acid) particle 100 weight parts, talcum micropowder 1 weight part that 6-hexamethylene diisocyanate is 0.4 μ m with adducts 1.5 weight parts, 1 weight part, 0.5 weight part, the median size of TriMethylolPropane(TMP) is supplied to quantitatively in Henschel mixer (L) and mixes, and supplies with a certain amount of to injection moulding machine (B) from nitrogen-sealed hopper (A).By the ram pump (E) of supplying with nitrogen side, with respect to poly (lactic acid) composition, inject 2 % by weight nitrogen, at 170 ℃ from the slit sizes shown in Fig. 1 for the nib portion (S) of 0.1mm in length and breadth and length 150mm take stroke within 30 seconds, be expressed into remain on the thickness of 40 ℃ as 10mm, the degree of depth as 90mm, cun in length and breadth in the box forming mould (P) of 100mm, manufacture injection-expansion molded product T1 of the present invention, T2, T3.The temperature, pressure of the nib portion in above-mentioned operation is about 170 ℃ of 8MPa, and the nitrogen in nib portion reaches supercritical state.Above-mentioned poly (lactic acid) composition, under this nitrogen is overcritical, utilizes the shearing force while extruding from nib portion mechanically to be pulverized, and foams by talcum powder simultaneously.
The expansion ratio of T1, T2, T3 is 22 times.Thermotolerance is all excellent.The MI value of measuring under load 21.6kg after T1, T2, T3 deaeration is respectively to 0.5,0.2,0.1.In addition, the GPC mensuration by T1, T2, T3 does not detect the more than 1,500,000 remarkable large high molecular thing of polystyrene conversion.
(embodiment 2) pearl and foam molded product
On the 50mm screw processing unit (plant) of making for No. 4044952 according to Japanese Patent, cutting machine in general water is installed and is used.The screw rod using in this device does not have nib groove, and this portion is used with the state of screw rod external diameter, inserts internal diameter and form nib than the sleeve of the large 0.2mm of screw rod external diameter in the barrel of this portion.In raw material poly(lactic acid) 100 weight parts that the MI value of manufacturing in Production Example 1 is 88 by 1 of Normal Atmospheric Temperature Liquid, 6-hexamethylene diisocyanate was supplied in hopper (A) with the coordinating with Henschel mixer (L) mix and blend batch of talcum micropowder 1 weight part that adducts 0.5 weight part, the median size of TriMethylolPropane(TMP) are 0.4 μ m, with respect to the poly (lactic acid) composition nitrogen of weight feed 0.2 % by weight intermittently, from nib, extrude, cooling in water, by cutting machine in water, obtain circular granular.In addition, similarly to Example 1, in nib portion, according to rare gas element (nitrogen), reach the mode design temperature pressure of supercritical state.By this particle at 80 ℃ in Vacuumdrier after dry 24 hours, pack keeping in the aluminium bag of nitrogen sealing into, manufacture poly (lactic acid) composition circular granular of the present invention.
Above-mentioned circular granular 100 weight parts and Trimethylmethane, 2: 1 solution 5 weight parts of methyl alcohol are put into autoclave, at 70 ℃, keep, after 1 hour, being cooled to normal temperature, manufacture expanded beads of the present invention.
The above-mentioned pearl of specified amount is put into mould water steam-heated cal(l)andria and within 1 minute, make its foaming, manufacture poly (lactic acid) composition foam molded product T4 of the present invention.The expansion ratio of this foam molded product is 28 times.Thermotolerance is all excellent.The MI value that this foam molding is measured under load 21.6kg is 0.2.By GPC, measure and the more than 1,500,000 remarkable large high molecular thing of polystyrene conversion do not detected.
(comparative example 1) injection expansion molding
For relatively, unload the nib portion (S) that gives shearing force of embodiment 1, other condition comparison product C1, C2, C3 identical and that manufacture are the expansion ratio lower than 5 times, and expansion ratio is partly inhomogeneous.Because expansion ratio is not elevated to prescribed value, so can not be shaped to box.By GPC, measuring polystyrene conversion surpasses more than 2,000,000 remarkable large high molecular thing is determined as 1 % by weight.
Infer this be due to, unloaded the nib portion (S) that gives shearing force, thus molecular weight significantly large poly (lactic acid) composition hindered the stretching of abscess film, so expansion ratio does not raise.
(comparative example 2) pearl foaming and molding
For relatively, remove the sleeve using in embodiment 2, insert than the sleeve of the large 2mm of screw rod external diameter and use.The comparison product that other condition and embodiment 2 manufacture for the same terms are the expansion ratio lower than 5 times, and expansion ratio is partly inhomogeneous.Because expansion ratio does not rise to prescribed value, so can not be shaped to box.By GPC, measuring polystyrene conversion surpasses more than 2,000,000 remarkable large high molecular thing is determined as 1 % by weight.
(comparative example 3) injection molding
Use the raw material poly(lactic acid) that the MI value under the load 2.16kg manufacturing in Production Example 1 is 800, similarly to Example 1, by 1, the MI value that the use level of the adducts of 6-hexamethylene diisocyanate and TriMethylolPropane(TMP) changes under the load 21.6kg of foam molded product C33 of 0.3 weight part is 8, viscosity deficiency and expansion ratio are low, can not be shaped to box.
(comparative example 4) is injection-expansion molded
Use the raw material poly(lactic acid) that the MI value under the load 2.16kg manufacturing in Production Example 1 is 88, similarly to Example 1, by 1, the MI value of load 21.6kg that the use level of the adducts of 6-hexamethylene diisocyanate and TriMethylolPropane(TMP) changes to the foam molded product C43 of 3 weight parts is 0.003, viscosity is too high and expansion ratio is low, can not be shaped to box.
(embodiment 3) injection-expansion molded product
Use the manufacturing system of the formation shown in Fig. 2.The processing machine forming with ram pump (E), aperture (S), foaming mould (P) is supplied with in use by Henschel mixer for mix and blend (L), hopper (A) for raw material supplying, injection moulding machine (B), foamed gas.
Use the easy processing machine system shown in Fig. 2, P0.5, P1, P1.5, the MI value of manufacturing in Production Example 1 is respectively by 1 of Normal Atmospheric Temperature Liquid in 800,420,88 raw material poly(lactic acid) particle 100 weight parts, talcum micropowder 1 weight part that 6-hexamethylene diisocyanate is 0.4 μ m with adducts 1.5 weight parts, 1 weight part, 0.5 weight part, the median size of TriMethylolPropane(TMP) is supplied to quantitatively in Henschel mixer (L) and mixes, and supplies with a certain amount of to injection moulding machine (B) from nitrogen-sealed hopper (A).From supplying with the side ram pump (E) of nitrogen, with respect to poly (lactic acid) composition, inject 2 % by weight nitrogen and 2: 1 mixed gass of methyl alcohol volume ratio, the nib portion (S) that it is 0.1mm in length and breadth and length 150mm that foaming mould Fig. 4 A of the hollow bulb state that is 0.2mm by thickness at 170 ℃ is expelled to the mold hole dimension shown in Fig. 1 remains in the foaming molding mold (P) of 100 ℃, the temperature of the poly(lactic acid) of injecting reaches after 100 ℃, as shown in Figure 4B, the thickness of the hollow bulb of mould is changed to 4mm, to make its foaming 30 seconds and to be full of after hollow bulb, by mold cools down to 40 ℃, kept for 30 seconds, manufacture injection-expansion molded product T11 of the present invention, T12, T13.In addition, the mode that reaches supercritical state according to the rare gas element in nib portion (mixed gas of nitrogen and methyl alcohol) is adjusted temperature and pressure.
With MI value under the load 21.6kg of the above-mentioned foam molding T33 of the present invention that similarly only talcum micropowder is changed to 0.3 weight part and manufacture be 0.1 constant, but thermotolerance is good.
The expansion ratio of T11, T12, T13 is 20 times.Thermotolerance is all excellent.The MI value of measuring under load 21.6kg of T11, T12, T13 is respectively 0.5,0.2,0.1.In addition, the GPC mensuration by T1, T2, T3 does not detect the more than 1,500,000 remarkable large high molecular thing of polystyrene conversion.
(embodiment 4) extrusion foaming sheet material
The system of processing of the structure being formed by connecting with T mould with general known sheet forming replaces the mould junctor (F) shown in Fig. 3, and foaming mould (P), in the raw material poly(lactic acid) particle P1.5 that the MI value of manufacturing in 100 weight part Production Examples 1 is 88 by 1 of Normal Atmospheric Temperature Liquid, adducts 1.5 weight parts of 6-hexamethylene diisocyanate and TriMethylolPropane(TMP), median size is that talcum micropowder 1 weight part of 0.4 μ m is supplied to continuously quantitatively in Henschel mixer (L) and mixes, from hopper (A) weight feed, from supplying with the ram pump (E) of nitrogen side with respect to the poly (lactic acid) composition nitrogen of weight feed 1.0 % by weight and methyl alcohol weight ratio 2: 1 intermittently, via the nib portion (S) that gives shearing force, take that to be cooled to the thickness of 100 ℃ be 0.5mm, width is that the sheet of 30cm is expressed in the sheet material extraction portion that is set as thickness 10cm that remains on 100 ℃.Keep the foaming and molding part in 30 seconds at 100 ℃ after, by the cooling segment of 40 ℃, to be cooled to than the state of low 5 ℃ of the Tg of poly(lactic acid), cut into certain length, manufacture foaming and molding sheet material of the present invention.In addition, according to the rare gas element in nib portion (mixed gas of nitrogen and methyl alcohol), reach the mode of supercritical state, adjust temperature and pressure.
The excellent heat resistance of this sheet material.The MI value that this foam molding is measured under load 21.6kg is 0.2.By GPC, measure and the more than 1,500,000 remarkable large high molecular thing of polystyrene conversion do not detected.
(comparative example 5) injection expansion molding
For relatively, unload the nib portion (S) that gives shearing force of embodiment 3, comparison product C1, C2, C3 that other condition is manufactured are in the same manner the expansion ratio lower than 5 times, and expansion ratio is partly inhomogeneous.By GPC, measuring polystyrene conversion surpasses more than 2,000,000 remarkable large high molecular thing is determined as 1 % by weight.
Infer this be due to, unloaded the nib portion (S) that gives shearing force, thus molecular weight significantly large poly (lactic acid) composition hindered the stretching of abscess film, so expansion ratio does not raise.
(comparative example 6) extrusion foaming is shaped
For relatively, unload the nib portion (S) that gives shearing force of embodiment 4, the comparison product C4 that other condition is manufactured is in the same manner the expansion ratio lower than 5 times, expansion ratio is partly inhomogeneous.Because expansion ratio does not rise to prescribed value, so can not be shaped to box.By GPC, measuring polystyrene conversion surpasses more than 2,000,000 remarkable large high molecular thing is determined as 1 % by weight.
(embodiment 5)
MI value under the load 21.6kg of the foam molding T33 of the present invention that similarly only talcum micropowder is changed to 0.3 weight part with the T3 of embodiment 3 and manufacture is 0.1 constant, but thermotolerance is good.
(embodiment 6)
Use the raw material poly(lactic acid) P0.5 that the MI value under the load 2.16kg manufacturing in Production Example 1 is 800, similarly to Example 3 by 1, the MI value that the use level of the adducts of 6-hexamethylene diisocyanate and TriMethylolPropane(TMP) changes under the load 21.6kg of foam molded product C33 of 0.5 weight part is 4.2, and thermotolerance is good.
(comparative example 7) extrusion foaming is shaped
The raw material poly(lactic acid) P0.5 that the MI value of using the load 2.16kg manufacturing in Production Example 1 is 800, similarly to Example 4 by 1, the MI value that the use level of the adducts of 6-hexamethylene diisocyanate and TriMethylolPropane(TMP) changes under the load 21.6kg of foam molded product C33 of 0.25 weight part is 7, find optimum condition, but expansion ratio terminates in 3.8 times.
(comparative example 8)
Use the raw material poly(lactic acid) that the MI value under the load 2.16kg manufacturing in Production Example 1 is 88, similarly to Example 2 by 1, the MI value that the use level of the adducts of 6-hexamethylene diisocyanate and TriMethylolPropane(TMP) changes under the load 21.6kg of foam molded product C43 of 3 weight parts is 0.003, viscosity is too high, is difficult for extruding and not finding suitable expansion ratio condition.
Nomenclature
1 top board
2 feeler gauges
3 press tables
A hopper: subsidiary weigh feeder, preferably through the device of nitrogen purge
B injection moulding machine: preferably there is ventilation hole and aspirate by vacuum pump in the way of forcing machine portion
G forcing machine: preferably there is ventilation hole on the way and aspirate by vacuum pump
E supplies with the ram pump of foamed gas side
L Henschel mixer: other the metering such as additive of poly(lactic acid), polyisocyanates, calcium carbonate or talcum is dropped into and the device of mix and blend, be preferably the device that can enclose nitrogen
P foaming mould: generally also use, but the mould of special construction describes in Instructions Page 10
S nib portion: formed by top board (1), press table (3), feeler gauge (2)

Claims (9)

1. a poly (lactic acid) composition, is characterized in that, it is by applying shearing force carry out the poly (lactic acid) composition that mechanical disintegration obtains under the super critical condition of rare gas element having carried out crosslinked poly(lactic acid) with polyisocyanates,
With respect to poly(lactic acid), the use level of described polyisocyanates is 0.4～5 % by weight,
The MI value that the poly (lactic acid) composition obtaining by described pulverizing is measured according to JISK7210 under 190 ℃, load 21.6kg is more than 0.05 and below 5.
2. poly (lactic acid) composition according to claim 1, is characterized in that, the poly (lactic acid) composition obtaining by described pulverizing, utilize the number-average molecular weight of the polystyrene conversion that GPC measures to be less than 1,500,000.
3. poly (lactic acid) composition according to claim 1 and 2, wherein, polyisocyanates is triisocyanate, tetraisocyanate or vulcabond, or any of the adducts that comprises described polyisocyanates.
4. poly (lactic acid) composition according to claim 1 and 2, wherein, the calcium carbonate that contains 0.5～5 % by weight or talcum particulate.
5. a foam molded product, it is formed by the poly (lactic acid) composition described in any one in claim 1 to 4.
6. foam molded product according to claim 5, after the hot water that its injection is 90 ℃, keeps form.
7. a manufacture method for poly (lactic acid) composition, is characterized in that, it is that it comprises as follows by applying to carried out crosslinked poly(lactic acid) with polyisocyanates the manufacture method that shearing force is carried out the poly (lactic acid) composition that mechanical disintegration obtains:
With respect to poly(lactic acid), the use level of described polyisocyanates is the operation of 0.4～5 % by weight,
The operation that described pulverizing is carried out under the super critical condition of rare gas element, and
The MI value that the poly (lactic acid) composition obtaining by described pulverizing is measured according to JISK7210 under 190 ℃, load 21.6kg is the operation more than 0.05 and below 5.
8. the manufacture method of a foam molded product, it is characterized in that, it is the method for manufacturing the foam molded product being formed by the poly (lactic acid) composition described in any one in claim 1 to 4, comprise following operation: use the device that possesses injection moulding machine or extrusion shaping machine, nib portion and foaming mould, under the super critical condition of foamed gas, in nib portion, apply shearing force, described poly (lactic acid) composition is carried out to mechanical disintegration.
9. a foam molded product, it is to manufacture by the manufacture method of claim 8.
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